WO2017009662A1 - Corps nanoporeux mis en forme - Google Patents

Corps nanoporeux mis en forme Download PDF

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Publication number
WO2017009662A1
WO2017009662A1 PCT/GB2016/052154 GB2016052154W WO2017009662A1 WO 2017009662 A1 WO2017009662 A1 WO 2017009662A1 GB 2016052154 W GB2016052154 W GB 2016052154W WO 2017009662 A1 WO2017009662 A1 WO 2017009662A1
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WIPO (PCT)
Prior art keywords
lignin
resin
carbon
particles
component
Prior art date
Application number
PCT/GB2016/052154
Other languages
English (en)
Inventor
Stephen Robert Tennison
Michal Kowalski
Thomas Avery
Susan Rachel Sandeman
Carol Angela Howell
Yishan ZHENG
Ganesh INGAVLE
Sergey Victorovich Mikhalovsky
Mambet NURALIYEV
Original Assignee
C-Tex Limited
University Of Brighton
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by C-Tex Limited, University Of Brighton filed Critical C-Tex Limited
Priority to US15/745,399 priority Critical patent/US10773234B2/en
Priority to ES16760135T priority patent/ES2968009T3/es
Priority to EP16760135.0A priority patent/EP3322518B1/fr
Publication of WO2017009662A1 publication Critical patent/WO2017009662A1/fr

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61M—DEVICES FOR INTRODUCING MEDIA INTO, OR ONTO, THE BODY; DEVICES FOR TRANSDUCING BODY MEDIA OR FOR TAKING MEDIA FROM THE BODY; DEVICES FOR PRODUCING OR ENDING SLEEP OR STUPOR
    • A61M1/00—Suction or pumping devices for medical purposes; Devices for carrying-off, for treatment of, or for carrying-over, body-liquids; Drainage systems
    • A61M1/34—Filtering material out of the blood by passing it through a membrane, i.e. hemofiltration or diafiltration
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61M—DEVICES FOR INTRODUCING MEDIA INTO, OR ONTO, THE BODY; DEVICES FOR TRANSDUCING BODY MEDIA OR FOR TAKING MEDIA FROM THE BODY; DEVICES FOR PRODUCING OR ENDING SLEEP OR STUPOR
    • A61M1/00—Suction or pumping devices for medical purposes; Devices for carrying-off, for treatment of, or for carrying-over, body-liquids; Drainage systems
    • A61M1/34—Filtering material out of the blood by passing it through a membrane, i.e. hemofiltration or diafiltration
    • A61M1/3472—Filtering material out of the blood by passing it through a membrane, i.e. hemofiltration or diafiltration with treatment of the filtrate
    • A61M1/3486—Biological, chemical treatment, e.g. chemical precipitation; treatment by absorbents
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61M—DEVICES FOR INTRODUCING MEDIA INTO, OR ONTO, THE BODY; DEVICES FOR TRANSDUCING BODY MEDIA OR FOR TAKING MEDIA FROM THE BODY; DEVICES FOR PRODUCING OR ENDING SLEEP OR STUPOR
    • A61M1/00—Suction or pumping devices for medical purposes; Devices for carrying-off, for treatment of, or for carrying-over, body-liquids; Drainage systems
    • A61M1/36—Other treatment of blood in a by-pass of the natural circulatory system, e.g. temperature adaptation, irradiation ; Extra-corporeal blood circuits
    • A61M1/3679—Other treatment of blood in a by-pass of the natural circulatory system, e.g. temperature adaptation, irradiation ; Extra-corporeal blood circuits by absorption
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
    • B01J20/28042—Shaped bodies; Monolithic structures
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
    • B01J20/28042—Shaped bodies; Monolithic structures
    • B01J20/28045—Honeycomb or cellular structures; Solid foams or sponges
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28054—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J20/28078—Pore diameter
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28054—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J20/28078—Pore diameter
    • B01J20/28083—Pore diameter being in the range 2-50 nm, i.e. mesopores
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28054—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J20/28078—Pore diameter
    • B01J20/28085—Pore diameter being more than 50 nm, i.e. macropores
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B01J20/3007—Moulding, shaping or extruding
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B01J20/3021—Milling, crushing or grinding
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B01J20/305—Addition of material, later completely removed, e.g. as result of heat treatment, leaching or washing, e.g. for forming pores
    • B01J20/3064—Addition of pore forming agents, e.g. pore inducing or porogenic agents
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B01J20/3078—Thermal treatment, e.g. calcining or pyrolizing
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/30—Active carbon
    • C01B32/354—After-treatment
    • C01B32/382—Making shaped products, e.g. fibres, spheres, membranes or foam
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2220/00—Aspects relating to sorbent materials
    • B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
    • B01J2220/48—Sorbents characterised by the starting material used for their preparation
    • B01J2220/4812—Sorbents characterised by the starting material used for their preparation the starting material being of organic character
    • B01J2220/485—Plants or land vegetals, e.g. cereals, wheat, corn, rice, sphagnum, peat moss
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2220/00—Aspects relating to sorbent materials
    • B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
    • B01J2220/48—Sorbents characterised by the starting material used for their preparation
    • B01J2220/4875—Sorbents characterised by the starting material used for their preparation the starting material being a waste, residue or of undefined composition
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/16—Pore diameter
    • C01P2006/17—Pore diameter distribution

Definitions

  • This invention relates to a method for producing complex shaped nanoporous materials through the use of lignin as a binder for pyrolysable precursors.
  • the green body is then further fired to pyrolyse the binder and this is then typically further activated in steam, air, carbon dioxide or mixtures of these gases to give the high surface activated carbon product.
  • the drawback to this route is that the binder, which is usually a thermoplastic material, goes through a melting transition prior to pyrolytic decomposition. At this point the material is weak and unable to support a complex form. This, combined with the problems of activating the fired body, typically limits the size and shape of the products to simple extrudates.
  • An alternative route is to take an activated carbon powder and form this directly into the final shape.
  • a range of polymeric binders have been used that remain in the final product.
  • the main drawback to this route is that high levels of binders are required and these then tend to both fill the pores of the activated carbon powder and encapsulate the powder, leading to a marked reduction in adsorption capacity and a deterioration in the adsorption kinetics.
  • the presence of the polymeric phase also degrades the physical and chemical stability of the formed material, severely limiting the range of applicability.
  • a further alternative is to take a formed ceramic material, such as a multichannel monolith, and to coat this with a carbon forming precursor such as a phenolic resin.
  • Monolithic porous carbon can be made by partially curing a phenolic resin to a solid, comminuting the partially cured resin, extruding the comminuted resin, sintering the extruded resin so as to produce a form-stable sintered product and carbonising and activating the form-stable sintered product.
  • EP 0 254 551 (Satchell et al., the contents of which are incorporated herein by reference) gives details of methods of forming porous resin structures suitable for conversion to porous carbon structures.
  • WO 02/072240 (Place et al.,. the disclosure of which is incorporated herein by reference) gives further details of producing monolithic structures using sintered resin structures of EP 0 254 551.
  • the resin cure is controlled so that it is sufficient to prevent the resin melting during subsequent carbonisation but low enough that the resin particles produced during the milling step can sinter during subsequent processing.
  • the amount of crosslinking agent and the temperature and duration of the partial curing step are selected as to give a degree of cure sufficient to give a sinterable product, and such that a sample of the partially cured solid when ground to produce particles in the size range 106-250 ⁇ and tableted in a tableting machine gives a pellet with a crush strength which is not less than 1 N/mm.
  • the pellet after carbonisation has a crush strength of not less than 8 N/mm.
  • the comminuted resin particles may have a particle size of 1-250 ⁇ , in embodiments 10-70 ⁇ .
  • the resin powder size is 20-50 ⁇ which provides for inter-particle channels of size of 4-10 ⁇ with an inter-particle channel volume of 30-40%.
  • the size of the particles is selected to provide a balance between diffusivity through the inter-particle voids and within the particles.
  • the milled powder can then be extruded to produce polymeric monolithic structures with a wide range of cell structures, limited only by the ability to produce the required extrusion die, or other forms such as rods, tubes, trilobes etc. Suitable dies are well known to those skilled in the art.
  • the monolith has a bimodal structure - the visible channel structure with either the central channel in a simple tube or the open cells in a square channel monolith of typically 100- 1000 ⁇ cell dimension and cell walls with thickness typically 100- ⁇ and the inter-particle void structure within the walls generated by the sintered resin particles.
  • Carbonisation takes place preferably by heating above 600°C for the requisite time e.g. 1 to 48 hours and takes place under an inert atmosphere or vacuum to prevent oxidation of the carbon.
  • the material loses about 50% weight and shrinks by about 50% volume but, provided the resin cure stage was correctly carried out, this shrinkage is accommodated with little or no distortion of the monolith leading to a physical structure identical to that of the resin precursor but with dimensions reduced by -30%.
  • the inter-particle void size is also reduced by -30% although the void volume (ml/ml) remains essentially unaltered.
  • the microstructure of the porous carbon develops, particularly at temperatures above 600°C. After carbonisation there may be partial blocking of the microstructure by the decomposition products from the carbonisation process. These blockages may be removed by activation to provide rapid access to the internal structure of the carbon that may be desirable for the operation of the monoliths as adsorption devices.
  • This production route is limited to the use of novolac resins and this in turn limits the pore structure that can be produced to the approximately lnm pores that are characteristic of all novolac derived carbons and larger macropores, typically greater than ⁇ , that are produced by the voids between the sintered particles. It is not possible by this route to produce products with pores in the large meso-small micro range of sizes.
  • the precursors typically comprising the novolac resin and the curing agent (typically hexamethylenetetramine (HTMA)) are dissolved in the pore forming solvent (typically ethylene glycol) in the ratios necessary to generate the required pore structure and degree of cure.
  • the mixture can either be cured by dispersing in hot oil to form beads or placed in trays and cured in an oven. In the latter case the block of cured resin is subsequently processed by milling to give either the finished powder or a precursor for extrusion.
  • the critical limitation of this route is that the strength, attrition resistance and control of porosity in the resulting monolith materials produced is insufficient to allow these materials to be used in demanding applications such as blood filtration.
  • One problem with which the invention is concerned is how to bind these highly cured porous resins, or other materials, into the structure to give a high strength, attrition- resistant structure.
  • lignin which is essentially a naturally occurring phenolic resin
  • lignin can be used as a binder phase with a wide range of second phases.
  • pitch as a binder
  • the use of lignin produces form-stable green materials which show little or no distortion on firing.
  • lignins can be used as binders for a wide range of nanoporous precursors, significantly expanding the range of controlled structure materials that can be produced.
  • ⁇ porous inorganic materials such as silicas, zeolites etc.
  • the route is particularly beneficial for polymeric (e.g. phenolic resins) or other biological precursors, for example waste organic materials such as hemp shives, flax waste, rice husks or any other lignocellulose derived material.
  • waste organic materials such as hemp shives, flax waste, rice husks or any other lignocellulose derived material.
  • the lignins have the further advantage that, as essentially naturally occurring phenolic resins, they are compatible and co-soluble with the novolac resins used in the formation of other phenolic resin derived carbons.
  • the lignin can also be stabilised by controlled oxidation. It is then possible for instance to make a monolithic structure from a pure lignin precursor. In this instance the lignin powder can be extruded as described above for the cured phenolic resin powder. After drying the monoliths are then placed in an air oven at ⁇ 300°C overnight. The monolith can then be pyrolysed as normal without the melt flow characteristic exhibited by the feed resin powder. A similar result can be achieved by controlled oxidation of the lignin precursor powder although this can be more difficult to control than oxidation of the formed monolith. It is also possible, and potentially beneficial, to use both pre and post oxidation.
  • the invention provides a method for producing a carbonisable shaped resin body which comprises:
  • the dough may be extruded to form a shaped body having walls defining a multiplicity of internal channels for fluid flow, the channels being directed along the extrusion direction.
  • the extruded structure may be carbonised and may be further activated by treating in flowing carbon dioxide at a temperature of at least 850°C, preferably 900°C for a time selected to give a required weight loss which may be at least 20%, preferably 25%.
  • the resulting carbonised material may be a square channel monolith of 100-1000 ⁇ cell dimension and cell walls with thickness 100-1000 ⁇ .
  • the cell density may be at least 600 channels per square inch e.g. at least 1000 channels per square inch.
  • the invention further provides a monolith structure which is an elongated body of carbon having walls defining a multiplicity of internal transport channels for fluid flow longitudinally through said body, the carbon comprising particles of microporous and mesoporous and/or macroporous carbon dispersed in a matrix of microporous carbon.
  • the present monolith structure may be the product of the method of any method described herein. It may be provided with a shrink wrap covering its longitudinal exterior surface for preventing in use leakage or escape of blood, serum or plasma.
  • a flow-through chamber may be provided for connection into extracorporeal blood treatment apparatus having a flow path for the extracorporeal blood, an inlet for the flow path at one end of the chamber, an outlet for the flow path at an opposed end of the chamber and arranged within the chamber for through-flow of extracorporeal blood a monolith structure as defined above.
  • the wall of the chamber may be of medical grade plastics material and seal to the ends of the monolith may be by compression members and O-rings or the like. It will be appreciated that a minimum of mechanical strength in the monolith is needed to resist the sealing and other forces encountered in manufacture of the through-flow chamber and in service.
  • the invention further provides extracorporeal blood treatment apparatus including a flow-through chamber as defined above.
  • a carbonised monolith comprising mesoporous and/or macroporous carbon particles dispersed in a matrix of microporous carbon particles with voids between the particles defining paths for fluid to flow into and through the structure.
  • the monolith may take the form of a shaped body having walls defining a multiplicity of internal transport channels for fluid flow, the transport channels being directed along the extrusion direction.
  • the monolith may be made by carbonising a shaped phenolic body based on phenolic resin precursors. In a method for producing such a carbonisable shaped resin body solid particles of a first phenolic resin are provided which is partially cured so that the particles are sinterable but do not melt on carbonisation.
  • the particles of the first phenolic resin are mixed with particles of a second phenolic resin that has a greater degree of cure than said first phenolic resin and has a mesoporous and/or macroporous micro structure that is preserved on carbonisation.
  • the resulting mixture is formed into a dough e.g. by mixing the resin particles with methyl cellulose and water, after which the dough is extruded to form a shaped product and stabilising in its shape by sintering.
  • the invention further provides carbon having mesopores and micropores/macropores in a bimodal pore distribution and derived by carbonisation of lignin and a novolac resin for use in the extracorporeal treatment of blood for any of:
  • the invention yet further provides a method of extracorporeal treatment of blood which comprises passing the blood in an extracorporeal circuit through a carbon monolith as defined herein for of any of:
  • the carbon monolith may for example be derived by extrusion of lignin and mesoporous particles of a cured novolac resin.
  • Figure 1 is a set of three diagrams and one photograph illustrating the structure of a monolith
  • Figure 2 is a photograph showing three carbon monoliths
  • Figure 3 is a table showing the composition of lignocelluloses as a function of the precursor
  • Figure 4A shows formulae for primary lignin components /?-coumaryl-, coniferyl- and sinapyl alcohols, dominant building blocks of the amorphous lignin polymer
  • Figure 4B is a model structure for spruce-derived lignin
  • Figure 5 shows the particle size distribution of jet-milled resin of Example 2
  • Figure 6 shows density as a function of pore former and HMTA content for the monoliths of Example 3 ;
  • Figure 7 shows the variation in mercury pore volume with HMTA content for the macroporous (TE7) powder and monoliths of Example 3;
  • Figure 8 shows 3 point bend test results for the extruded rods of Example 4 and in particular the impact of cured resin content and degree of cure of the microporous resin content on strength of the carbonised extrudate;
  • Figure 9 shows the effect of binder resin cure on the pore structure of the monoliths
  • Figure 10 compares the strength and porosity as a function of binder resin concentration
  • Figure 11 shows the impact of lignin binder content on monolith pore structure and compares this with the pore structure of a resin bound monolith
  • Figure 12 shows a comparison of theoretical pore volume based on lignin dilution with observed pore volume
  • Figure 13 shows the change in crush strength and weight loss on carbonisation as function of the lignin:resin ratio ;
  • Figure 14 is a photograph of a 100% lignin monolith after pyrolysis;
  • Figure 15 shows the nitrogen pore size distribution of bead carbons as a function of the ethylene glycol pore former (E3 to E6) concentration for a pure novolac resin precursor (ethylene glycol modified J1098F novolac resin);
  • Figure 16 shows the nitrogen pore size distribution of beads produced from varying resin:organosolv lignin (OSL) ratios and a low ethylene glycol (EG) pore former concentration (E3);
  • OSL resin:organosolv lignin
  • EG ethylene glycol
  • Figure 17 shows the nitrogen pore size distribution of beads produced from varying resin:organosolv lignin (OSL) ratios and an intermediate ethylene glycol (EG) pore former concentration (E5);
  • OSL resin:organosolv lignin
  • EG intermediate ethylene glycol
  • Figure 18 is a schematic of a monolith cross section showing the definition of the unit cell and three shadow graphs showing the actual cross section of 7mm, 600 and 1300 CPI monoliths and a 30mm 600CPI monolith;
  • Figure 19 shows the nitrogen adsorption isotherms for a rage of rice husk-lignin based monoliths
  • Figure 20 is a block diagram showing a whole blood or plasma perfusion system for small monoliths
  • Figure 21 is a graph showing the removal of IL-6 from plasma using the lignin bound monolith and the test system in Figure 20;
  • Figure 22 shows removal of IS using lignin bound monoliths.
  • Figure 23 shows the PCS (p-cresyl sulphate) remaining in the plasma sample after 5, 30, 60 and 120 minutes of circulation through monoliths: TE7/Lignin (90-10) (inverted triangles), TE7/Lignin (75-25) (triangles), TE7/Micro (50-50) (circles) and TE7/Lignin (50-50) (squares).
  • Figure 24 shows the removal of spiked cytokine marker IL-6 from human plasma pool by carbon monoliths.
  • A the IL-6 removal expressed as percentage of IL-6 concentration at time 0;
  • B the removal of IL-6 is expressed as ng of IL-6 adsorbed by each gram of activated carbon;
  • Figure 25 shows the removal of spiked albumin bound uraemic toxin marker PCS from human plasma pool by carbon monoliths.
  • Figure 26 shows the removal of spiked albumin bound uraemic toxin marker indoxyl sulphate (IS) from human plasma pool by carbon monoliths.
  • IS spiked albumin bound uraemic toxin marker indoxyl sulphate
  • Figure 27 shows the adsorption of IL-6 and TNF from plasma in 30mm diameter lignin bound monolliths
  • Figure 28 shows adsorption of PCS and IS from circulating plasma using 30 mm lignin bound monoliths
  • Figure 29 shows adsorption of PCS, IS, IL-6 and TNFa from whole blood using 30 mm monoliths
  • Figure 30 shows adsorption of Staphylococcal enterotoxin B (SEB) from human plasma using carbon beads with lnm pores (carbon 1), 30nm pores (Carbon 5) and lOOnm pores (carbon 9);
  • SEB Staphylococcal enterotoxin B
  • Figure 31 shows the amount of tryptophan removed from the spiked human plasma.
  • Figure 32 shows the adsorption kinetics of bilirubin by AC 1-5 from spiked plasma.
  • the adsorption kinetics of bilirubin by 0.4 ml microporous carbon (Al), mesoporous carbon (A2) and macroporous carbon (A3, A4 and A5) from 5.6 ml 300 ⁇ bilirubin spiked plasma was observed at 4 time points over 60 min of incubation period. (Mean n 5, + SEM); and
  • Figure 33 shows the reduction in Bilirubin content of circulating blood of a bile duct ligation (BDL) animal model of liver failure during haemoperfusion using a macroporous carbon monolith (upper line) and sham control (lower line).
  • BDL bile duct ligation
  • microporous refers to a carbon or other material possessing pores with diameter ⁇ 2 nm, as measured by nitrogen adsorption and mercury porosimetry methods and as defined by IUPAC.
  • mesoporous refers to a carbon or other material possessing alongside micropores, pores with diameter from ca. 2 nm to ca. 50 nm, as measured by nitrogen adsorption and mercury porosimetry methods and as defined by IUPAC.
  • macroporous refers to a carbon or other material possessing alongside micropores and mesopores , pores with diameters larger than 50 nm. This is preferably measured by mercury porosimetry methods and as defined by IUPAC, comprises pores of greater than 50nm diameter.
  • monolithic is meant that the resulting porous carbon is in a single piece i.e. not granular or not composed of granular carbons bound together by a binder, for instance a polymer etc. and is composed entirely of carbon.
  • the monolithic carbon may contain large transport channels in addition to inter-particle voids within the walls of the transport channels and the macro/meso/microporosity of the individual particles.
  • a continuous channel structure is defined by a channel dimension, W, and a wall thickness, t, or for an asymmetric monolith by channel length and width or other relevant dimensions as well as wall thickness t.
  • the walls of monolithic carbon have a void structure providing paths for fluid to flow into and through the carbonaceous body of the monolith.
  • the product can be formed as a moulded or extruded structure with similar micro and macro pores but lacking the channel structure.
  • Figure 2 shows the actual structure of three carbonised monoliths of ⁇ 7, 20 and 30mm diameter.
  • inter-particle voids are spaces formed within a structure that has been created by sintering solid partially cured resin particles and carbonising and activating the resulting sintered material.
  • Such voids may have sizes of the order of about 5 ⁇ but typically is -20% of the size of the powdered resin used to produce the monolith.
  • sintering we mean a step which causes the individual particles of phenolic resin to adhere together without the need for a separately introduced binder, while retaining their individual identity to a substantial extent on heating to carbonisation temperatures. Thus the particles must not melt after forming so as to produce a molten mass of resin, as this would eliminate the internal open void structure of the article. Even partial melting can degrade the form of the monolithic structure.
  • the open void structure (as opposed to the closed cells found in certain types of polymer foams) is believed to be important in enabling formed particles to retain their shape on carbonisation.
  • the lignins are a major component of all plant (lignocellulosic) materials. Plants comprise crystalline cellulose, hemi (amorphous) cellulose and lignin. The proportion of the three components varies with the precursor which range from grasses, plants such as hemp to hard and soft woods. Typical compositions are shown in 3.
  • Lignin is an amorphous copolymer of phenyl propene units formed via a radical copolymerisation of coumaryl alcohol, coniferyl alcohol and sinapyl alcohol ( Figure 4A).
  • Figure 4B The three dimensional nature of a soft wood (spruce) derived lignin is shown schematically in Figure 4B.
  • lignin is essentially a naturally occurring, medium molecular weight phenolic resin where the thermoplastic behaviour is a function of the composition which in turn depends on the precursor. As such it gives a high carbon yield on pyrolysis which is critical to achieve the good binder performance we have observed. Surprisingly however the binder performance is significantly enhanced when compared with synthetic phenolic resins of similar molecular weight. Whilst not wishing to be bound by the explanation the applicants believe that this is due to different melt flow characteristics of the two materials. As such the performance of the lignin materials in the processes described in this specification will be influenced by the melt flow and therefore by the precursor material.
  • lignin is generally a waste by-product of bio-refining and paper making where cellulose is generally the desired component.
  • lignin is generally produced as the acidic black liquor although it is also produced as a relatively pure material by for instance the Organosolv process (US Patent 3,585,104 Kleinert) which is used to extract the lignin in solution which is then precipitated.
  • the lignin from the traditional Kraft process cannot be used in the process of this invention due to the high level of contaminants but more critically its water solubility which precludes the use of a conventional aqueous extrusion processes.
  • the preferred material is produced by processes such as Organosolv and is a high purity water-insoluble powder that can be used in extrusion and other forming processes. In particular its metal content is low, preferably only a few ppm.
  • the Organosolv process involves digesting subdivided fibrous plant material in a digester at an elevated digesting pressure and at an elevated digesting temperature without pre-impregnation of pulping agent.
  • aqueous mixtures of the lower aliphatic alcohols such as methanol, ethanol, propanol
  • aqueous mixtures of the lower aliphatic ketones such as acetone
  • aqueous mixtures containing both lower aliphatic alcohols and lower aliphatic ketones are appropriate pulping agents, aqueous mixtures of ethanol in the range 20% - 75 wt% ethanol being preferred.
  • the claimed process comprises:
  • An advantage for this invention is that the cost of the lignin, essentially a waste material, is lower than synthetic oil derived phenolic resins. It can also be available in very large quantities.
  • a further advantage of lignin in this invention is that as it is essentially a naturally occurring phenolic resin the carbon yield during pyrolysis is high, typically around 30%. This is lower than that achieved with the synthetic phenolic resin, primarily reflecting loss of the side chains, but is none the less significantly higher than the ⁇ 20% yield typically achieved with cellulosic precursors.
  • the invention is concerned with the production of complex structures that can be extruded or moulded and comprise a range of precursor particles combined with lignin either as the binder (first phase) or as the main structural component.
  • the lignin can be used in combination with porous resin structures produced by methods such as those disclosed in US 8383703. In this case the similar carbon yield and volume shrinkage of the lignin binder and resin matrix components gives good strength at a low binder level, maximising the mesoporosity in the finished carbon.
  • the lignin can also be used in conjunction with a wide range of inorganic materials, such as zeolites and silicas, and other activated carbon powders but is limited to precursors with sufficient thermal stability to withstand the firing process. However in the case of the inorganic materials, which do not shrink during the firing process, the strength is reduced.
  • activated carbon materials from the lignin as the main, second phase either by the inclusion of phenolic resins in the starting mixture, which inhibit the melt flow characteristics of the lignin, or by oxidation stabilisation of the lignin whereby it is possible to produce structured materials from 100% lignin.
  • phenolic resins in the starting mixture, which inhibit the melt flow characteristics of the lignin, or by oxidation stabilisation of the lignin whereby it is possible to produce structured materials from 100% lignin.
  • the binder concentration should be adjusted to give the maximum strength and attrition resistance consistent with maintaining the maximum concentration, and therefore pore structure properties, of the second phase.
  • the second phase may also be a naturally occurring material prepared from e.g rice husk, flax waste or any other naturally occurring precursor.
  • the allowed binder content be higher, consistent with the production of mechanically stable product, as the goal is to make a low cost monolithic structure.
  • the pore structure derives primarily from the second phase which tends to be more reactive.. Some porosity does however derive essentially from carbonisation of the lignin component
  • the second phase is pyrolysable. It is also possible to use a non pyrolysable second phase such as activated carbon or a porous inorganic material such as a zeolite. In this instance the lack of shrinkage in the second phase still leads to mismatched shrinkage. This will give inferior mechanical properties which could necessitate the use of higher lignin binder levels
  • melt flow characteristics can be totally inhibited by either pre- oxidising the lignin powder and then extruding this normally or by forming the monolithic structure from as received lignin powder and then post oxidizing the extruded structure prior to carbonisation. In both cases the product carbon comprises 100% of the lignin precursor.
  • the active carbon component in the monolithic structures has the same micro : meso/macro binary pore structure that has been shown to be the critical component in the bead carbons used in extra-corporeal blood processing (Howell CA, Sandeman SR, Phillips GJ, Lloyd AW, Davies JG, Mikhalovsky SV, Tennison SR, Rawlinson AP, Kozynchenko OP, Owen HLH, Gaylor JDS, Rouse JJ, Courtney JM.
  • the in vitro adsorption of cytokines by polymer-pyrolysed carbon, Biomaterials, 27 (30): 5286-91 (2006)) and the examples later in this document demonstrate similar adsorption properties for the small, middle and larger molecule weight molecules.
  • the monolith in this instance would be used to augment current renal replacement therapies such as haemodialysis, to remove uraemic toxins that are currently poorly removed.
  • These applications are critically dependent upon the bimodal - micro plus meso/macro porous structure of the monoliths to achieve the removal of molecules with molecular weights ranging from 100' s to 56000, whilst having mechanical properties that prevent the shedding of carbon particles into the blood stream.
  • Mesoporous monoliths of this invention are able to remove a range of uraemic toxins from plasma and blood including; the albumin bound toxins indoxyl sulphate and p-cresyl sulphate which remain in the blood after haemodialysis and have been linked to progression of CKD, the high morbidity and mortality rates for end stage renal disease (ESRD) and cardiovascular disease (CVD).
  • the monoliths are also able to remove larger sized biotoxins such as the inflammatory cytokines and other contrary substances linked to ESRD.
  • Acute-on-chronic liver failure is characterised by a rapid loss of function in up to 90% of a patient's liver cells.
  • Extracorporeal liver support devices could detoxify the blood of ACLF patients and act as a bridge to transplantation.
  • the carbon monoliths are designed to adsorb small and medium- sized hydrophobic molecules (e.g. cytokines) that cannot be removed by conventional water-based dialysis.
  • the controlled pore structure carbons are also effective at removing the albumin bound liver toxins which include tryptophan, cholic acid and bilirubin. To date these tests have only been carried out using the bead form carbons which demonstrate clearly the critical role of pore structure.
  • the carbon must contain both the larger pores necessary for the complex to initially become associated with the carbon and then for the smaller pores to adsorb the toxin. This toxin adsorption is then related to the size and shape of the toxin and the structure of the micropores.
  • Bilirubin 584.66 9.5xl0 7 This is discussed in more detail in example 12.
  • SIRS systemic inflammatory response syndrome
  • the carbon beads have been shown to be successful in removing a range of inflammatory cytokines including TNF, IL-6 and IL-8 as well as both bacterial endotoxin and exotoxins from blood. This work has shown that the monoliths can also remove TNFa, the most difficult of the SIRS related molecules to remove, from both blood and plasma
  • Alcohol poisoning is a significant problem, particularly in the countries of the former Soviet Union.
  • lignin can be beneficially be used as a binder (second component) for a wide range of first components comprising preferably polymer materials that can be co-pyrolysed with the lignin.
  • first components comprising preferably polymer materials that can be co-pyrolysed with the lignin.
  • the first component comprises:- (1) Polymeric materials that provide a good yield of nanoporous carbon, for instance but not limited to phenolic resin. In this instance the shrinkage of the first and second component is similar and the strength in the final carbon is maximised.
  • Lignocellulosic materials and derivatives such as wastes from the processing of hemp, rice, wood etc. that produce carbon on pyrolysis but where the weight yield of the second component is lower, the shrinkage is therefore higher and the strength of the final material is therefore reduced.
  • Nanoporous materials such as activated carbons.
  • the second component does not shrink on thermal processing.
  • the nanopore structure of these materials is already formed and the temperature required to stabilise the lignin binder can be reduced substantially, limited only by final use considerations.
  • the method of production of the structured composite material is the same. This can be by either extrusion or pressurised moulding.
  • the first component preferably with a particle size between 20 and 100 ⁇ is mixed with between 10 and 40% volume of the lignin binder powder (second component) along with the extrusion aids.
  • the extrusion aids are well known to those skilled in the art but comprise primarily cellulose compounds such as Methocel, polyethylene oxide and other additives used to modify and control the rheology of the dough and water. The amount of water to be added depends on the porosity of the first component but should be sufficient to give a flexible dough.
  • Embodiments of present materials incorporate a wide range of pore structures depending on the nature of the first component.
  • the first component is the resin powder produced by solvent pore forming
  • the final material contains both micropores and relatively large mesopores (20-50nm) and optionally macropores (>50nm).
  • a precursor resin formulation is used which comprises a proportion of pore former off for instance 250 parts ethylene glycol to 100 parts of resin-forming components.
  • This provides macropores that are useful e.g. for adsorption of peptides and proteins e.g. cytokines in blood.
  • Larger macropores in carbonised and optionally activated material of size e.g. 200-2000nm arise from voids between the sintered particles of resin precursor and provide pathways for gas or liquid to permeate into the structure, but do not adsorb protein.
  • the final pore structure reflects the structure that would be derived by pyrolysis of these materials alone combined with the micropore structure that derives from the lignin binder.
  • Resins for making carbonaceous material can be prepared from any of the starting materials disclosed in WO 02/12380.
  • Nucleophilic components may comprise phenol, bisphenol A, alkyl phenols e.g. cresol, diphenols e.g. resorcinol and hydroquinone and aminophenols e.g. m-amino-phenol.
  • a phenolic novolac or other similar oligomeric starting material which, because it is already partly polymerised, makes the polymerization to the desired resin a less exothermic and hence more controllable reaction.
  • the preferred novolacs have average molecular weights (AMW) in the range of from 300 to 3000 prior to cross -linking, corresponding to a degree of polymerisation (DP) with respect to phenol of about 3-30 and may be solids with melting points in the region of 100°C.
  • AMW average molecular weights
  • DP degree of polymerisation
  • Novolac resins of AMW less than 2000 and preferably less than 1500 form resins which on carbonisation tend to produce carbons with desired pore size distributions using lower amounts of pore former.
  • Novolacs are thermally stable in that they can be heated so that they become molten and cooled so that they solidify repeatedly without structural change. They are cured on addition of cross-linking agents and heating. Fully cured resins are infusible and insoluble
  • modifying reagents Whilst commercial novolacs are largely produced using phenol and formaldehyde, a variety of modifying reagents can be used at the pre-polymer formation stage to introduce a range of different oxygen and nitrogen functionalities and cross- linking sites. These include but are not limited to: -
  • Diphenols e.g. resorcinol and quinone derivatives e.g. hydroquinone. Both are more reactive than phenol and can lead to some cross-linking at the pre-polymer production stage. It is also possible to introduce these compounds at the cross-linking stage to provide different cross-linking paths. These also increase the oxygen functionality of the resins.
  • Nitrogen containing compounds that are active in polycondensation reactions such as urea, aromatic (aniline, m-amino phenol) and heteroaromatic
  • the nucleophilic component may be provided alone or in association with a polymerisation catalyst which may be a weak organic acid miscible with the novolac and/or soluble in the pore former e.g. salicylic acid, oxalic acid, phthalic acid or / ⁇ -toluene sulfonic acid (but preferably not for resins intended to be carbonied as the addition of sulphur-containing compounds is undesirable).
  • a polymerisation catalyst which may be a weak organic acid miscible with the novolac and/or soluble in the pore former e.g. salicylic acid, oxalic acid, phthalic acid or / ⁇ -toluene sulfonic acid (but preferably not for resins intended to be carbonied as the addition of sulphur-containing compounds is undesirable).
  • the concentration of novolac in the pore former may be such that when combined with the solution of cross-linking agent in the same pore former the overall weight ratio of pore former to (novolac + crosslinking agent) is at least 125: 100 by weight.
  • the actual ratios of novolac:pore former and crosslinking agent:pore former are set according to convenience in operation e.g. in the case of the process disclosed in WO 2008/043983 (Tennison) by the operational requirements of a bead production plant and are controlled by the viscosity of the novolac:pore former solution such that it remains pumpable and by the ratio of crosslinking agent:pore former such that the crosslinking agent remains in solution throughout the plant.
  • the cross-linking agent is normally used in an amount of from 5 to 40 parts by weight (pbw) per 100 parts by weight of the nucleophilic components e.g. novolac, typically from 10 to 30 (e.g. 10, 15 or 20) pbw cross-linking agent per 100 pbw of nucleophilic component. It may be, for example, an aldehyde e.g. formaldehyde or furfural or a polyamine e.g. HMTA, melamine or hydroxymethylated melamine. HMTA is preferably used as cross-linking agent.
  • HMTA for a partially cured and sinterable resin material there may be employed up to 5 pbw of HMTA per 100 pbw of novolac. However for the production of the mesoporous/macroporous resin it is essential that the resin is fully cured. HMTA or other cross-linking agents are preferably used at a proportion of 15 to 25 pbw. Whilst the stoichiometric amount required for complete curing is approximately 15%, a level of 20% is preferably used to guarantee full curing. This ensures formation of the solid resin with maximal cross-linking degree and ensures the stability of the mesopore structure during subsequent removal of the pore former. At lower degrees of cross linking the structure tends to collapse during removal of the pore former prior to pyrolysis.
  • the pore former also acts as solvent.
  • the pore former is preferably used in sufficient quantities to dissolve the components of the resin system, the weight ratio of pore former to the total components of the resin system resin being preferably at least 1.25: 1.
  • the pore former may be, for example, a diol, a diol-ether, a cyclic ester, a substituted cyclic or linear amide or an amino alcohol e.g. ethylene glycol, 1,4-butylene glycol, diethylene glycol, triethylene glycol, ⁇ -butyrolactone, propylene carbonate, dimethylformamide, N- methyl-2-pyrrolidinone and mono ethanolamine, ethylene glycol being preferred, and where the selection is also limited by the thermal properties of the solvent as it should not boil or have an excessive vapour pressure at the temperatures used in the curing process.
  • the pore former In the presence of a low level of pore former the pore former is compatible with, and remains within, the cross-linked resin domains, (e.g., ⁇ 120 parts/100 parts Novolac for the Novolac-HMTA-Ethylene Glycol reaction system), whilst the remainder forms a solution with the partially cross-linked polymer between the domains.
  • the pore former adds to the light polymer fraction increasing the volume of material in the voids between the domains that gives rise to the mesoporosity and optionally macroporosity.
  • the higher the pore former content the larger the wider the mesopores up to macropores and the higher the pore volume.
  • This phase separation mechanism provides a variety of ways of controlling the pore development in the cross-linked resin structures. These include chemical composition and concentration of the pore former; chemical composition and quantity of the cross-linking electrophilic agents, presence, chemical nature and concentration of modifying nucleophilic agents, chemical composition of phenolic nucleophilic components (phenol, novolac), presence, chemical nature (acidic, basic), the presence of water within the solvent and concentration of any curing catalyst if present.
  • the pore former should also, in the case of phenolic resins, be compatible with water and/or other minor condensation products (e.g. ammonia) which are formed by elimination as polymerization proceeds, and the pore former is preferably highly miscible with water so that it can be readily removed from the polymerized resin by washing.
  • minor condensation products e.g. ammonia
  • a resin powder is required with a mean particle size of 20 to 100 ⁇ , preferably around 40 ⁇ .
  • This is manufactured by producing a mixed solution of the resin component and the cross linking agent in the pore forming solvent.
  • This typically comprises a medium molecular weight novolac, although the molecular weight is not critical, and HMTA dissolved in the pore forming solvent, preferably ethylene glycol (EG).
  • EG ethylene glycol
  • a critical requirement for the pore forming solvent is that it dissolves both the resin and crosslinking agent.
  • the two cold solutions are then mixed.
  • the novolac:HEX composition is 100 parts:20 parts whilst the ratio of EG: HEX+novolac is increased to increase the meso/macro pore volume.
  • the mixed solution is then cured which requires a temperature of approximately 150°C. This can either be in batch mode, where the mixture is poured into trays and then placed into a preheated oven, and which gives rise to blocks of cured resin which then require granulation, or in a continuous rotary oven where the product may be large granules.
  • the glycol can be removed by washing or vacuum drying and the particle size of the cured resin for washing is preferably a l-2mm which can be produced by granulation.
  • Standard monoliths of carbon produced from phenolic resins by existing processes have a microporous/inter-particle macroporous void structure and introduction of mesoporosity or macroporosity in the individual particles of resin precursor and then of carbon was not initially intended.
  • Forming monoliths having mesoporosity or macroporosity intentionally introduced into the structure of the individual particles from which the monolith is formed gives rise to a number of difficulties. Normally to produce the microporous monoliths it is necessary that the partially cured resin should be in a sinterable state, and that requirement limits the amount of cross-linking agent that can be used.
  • the meso/macro porous structure of the individual particles can only be stabilised by complete cure, typically using at least 15 parts of HMTA and preferably 20 parts curing agent per 100 parts resin. This material cannot be adequately sintered and it is therefore essential to use a separate binder component.
  • the lignin typically at between 10 and 30% weight loading is mixed with the meso/macro porous resin power described above.
  • the extrusion aids comprising materials well known to those skilled in the art, but comprising primarily methyl cellulose and polyethylene oxide, are mixed with the precursor powder and lignin powder. Water is then added to produce a pliable dough. The resulting dough can then be moulded or extruded and then dried. At this stage the resulting green body is fired to a minimum of 500°C, preferably greater than 700°C which is required to decompose the extrusion aids which at lower temperatures tend to block the pore structure.
  • the cell geometries that have been produced are limited at the high cell density end of the spectrum by the pressure drop through the monolith when in use, especially when using complex, high viscosity fluids such as blood but also the by the ability to produce the fine channel and hole structure in the extrusion die and the pressures required to actually extrude the dough.
  • the geometry at the low cell density end of the spectrum is limited by the performance of the carbon monolith in the separation process. We have shown that the separation performance drops rapidly at below approximately 600cpi.
  • the structures of the monoliths produced and tested in this application are summarised below for the three typical monoliths that have been used with nominal carbon diameters of 7, 20 and 32mm.
  • a key factor here is the monoliths shrink by approximately 30% radially and axially. This results in a significant increase in cell density between the extruded resin monolith as can be seen for the 7.9mm monolith where the cell density in the resin is 645 but in the carbon is 1315.
  • the transformation of the lignin bound structures into nanoporous structures is performed by carbonisation, i.e. high temperature treatment in an inert atmosphere and at temperatures from ⁇ 500°C upwards and where necessary activation.
  • the pyrolysis process begins at about 400°C and is largely complete by around 700°C although further small weight losses continue up to around 1400°C.
  • surface area development in the polymeric components is only significant above around 700°C at which point the material is not strictly carbon but a pyropolymer.
  • the inert atmosphere for pyrolysis can be secured by flowing suitable inert gas. Nitrogen and argon can be used as inert purge gases at any temperature whilst carbon dioxide is effectively inert up to around 800°C in the absence of catalytic metals.
  • Vacuum may also be used. Due to the presence of mesopores in these materials, which provide efficient escape routes for the volatile products, the heating rates employed can be very high - up to 10°C per minute.
  • the porosity of the carbon component can be further enhanced by conventional activation methods, e.g. by activation in carbon dioxide above 800°C, which can give surface areas as measured by BET 5 point method of up to 2000 m 2 /g or even up to 3000 m 2 /g. It has been found that "physical" activation with carbon dioxide at the temperatures in the range 850 - 900°C gives rise predominantly to microporosity
  • the walls of the resulting monolithic carbon have a structure with voids between the particles, the individual continuous void space leading into and through the monolith.
  • the void structure in the walls of a monolith is controlled by the particles used to form the monolith.
  • the monolith is made from macro-particles with a mean particle size of Dp ( Figure 5) the macro pore size is typically 20% of the size of the precursor mean particle size.
  • the sizes of the individual particles can be varied over a wide range from a maximum particle size of approximately 10% of the wall thickness, t, to a minimum practical particle size of about ⁇ . This gives a void size within the wall for a 1mm wall thickness of 2-20 ⁇ .
  • the void size fixes the bulk diffusivity of the adsorbent molecules within the matrix.
  • the monoliths are square channel monoliths with a cell structure (cells per square cm) where the channel size is between 100 and 2000 ⁇ and the wall thickness is between 100 and 2000 ⁇ and with an open area of between 30 and 60% to give a good carbon packing density per unit volume and acceptable mass transfer characteristics.
  • TE7/20 resin block was prepared as follows. 2841 g of ethylene glycol was mixed with 4315 g of 66.7% novolac resin in ethylene glycol after which HMTA (570 g) in 4276 g ethylene glycol was added to the mixture and stirred. The liquid mixture was then transferred to two metal trays. These were placed in the oven and ramped to 150°C at 3°C/min at which temperature they were held for 2 hours. During curing ammonia was released which was trapped in a water scrubber. After curing the block of resin was granulated to give approximately 2mm pieces which were suitable for water washing to remove the glycol. After washing and drying the resin granules were jet milled using a Hosokawa 100 AFG mill to give a powder with mean a particle size of 40 ⁇ . The particle size distribution is shown in Figure 5.
  • Example 3 Reference
  • a matrix of compositions was prepared by producing a mixed solution of the novolac resin and HMTA in the glycol solvent. This was placed in trays and cured at 150°C for 2 hours, after which it was crushed, water washed to remove the glycol and then milled to a fine powder ( ⁇ 100 ⁇ ) ( Figure 5). This was then mixed with water and cellulose ether (Methocel) and extruded into 3mm rods. After drying at room temperature the rods were carbonised at 80°C in flowing carbon dioxide. The density of the carbonised monoliths is shown in Figure 6.
  • Rods were produced using the fully cured mesoporous resin as the main component of the matrix and non-porous phenolic resin with varying degrees of cure as the binder matrix.
  • the binder phase comprised a standard novolac resin cured using either 3 parts or 5 parts weight HTMA (or used in its uncured state.
  • the partially cured resins were prepared by co-milling either 3 or 5 parts of HTMA and novolac (J 1098) powder. The mixed powder was then cured in small quantities at 150°C for 2 hours after which it was re-milled to ⁇ 100 ⁇ .
  • the rods were formed by nixing these milled resin powders with the milled mesoporous resin powder, forming this into a dough using water and Methocel and extruding this into 3mm rods.
  • the rods were dried at room temperature and were then carbonised at 800°C in flowing carbon dioxide.
  • the 3 -point bend test results are shown in Figure 8 and show the impact of cured resin content and degree of cure of the microporous resin binder on strength of the carbonised extrudate. It is apparent that the strength increases significantly with the binder resin content at levels higher than ⁇ 35%wt. It can also be seen that for the uncured resin which melt flows prior to carbonisation there is little improvement in strength until binder levels greater than 55%. This believed to be due to the loss of the binder into mesopores of the fully cured resin component.
  • Figure 9A shows the impact of the using the 5pt HMTA cured resin as the binder
  • Figure 9B shows the impact of using the uncured novolac resin as the binder. It can be seen that at 50% binder addition, there has been a -40% loss in porosity using the cured resin binder but an 80% porosity loss with the uncured novolac binder. It can be seen that for the 5% HTMA (HMTA5) structures the loss in porosity is greater than would be expected from dilution alone.
  • the pore volume should have reduced 1 to 0.5cm 3 /g whereas it was reduced to 0.35cm 3 /g.
  • the loss was even greater to 0.2cm 3 /g suggesting significant melt flow and pore filling of the porous resin component.
  • IS is m .:
  • the monoliths were extruded using a 7.5mm die with 600 cells per square inch (cpi).
  • the extruded TE7/Micro (50/50) monoliths showed a yellow colour, many areas of the monoliths had cracks on the outer surface indicating that the dough was not optimal for extrusion processes.
  • the monoliths were dark brown and with increased lignin content, the brown colour intensified. Most importantly, with increase of lignin content, cracks on the monolith outer surface disappeared, and the resulting dried monoliths had smooth outer surface.
  • the mercury pore size distributions for the materials are shown in Figure 11. These plots have been truncated at lOOOnm as the intrusion volume above this size is related to the inter-particle voids rather than the internal porosity of the spheres.
  • the internal pores have a size of 55nm irrespective of the lignin loadings.
  • Figure 12 shows the pore volume in the 10-lOOOnm pore size range.
  • the diamond-pattern points are the measured pore volumes whilst the square pattern points are the expected pore volume based simply on dilution of the mesoporous resin with the microporous lignin derived material. This demonstrates that the lignin does block some of the desired mesopores although the loss is acceptable at less than 25% lignin.
  • Figure 13 shows the crush strength of the lignin bound mesoporous structures. At the lower levels of lignin (lignin as the binder) it can be seen that from approximately 25 to 55% weight lignin there is a plateau with acceptable crush strength of ⁇ 3Kg. Below 25% binder the strength drops rapidly. Taking account of the pore volume loss shown in Figure 10 it can be seen that around 25% lignin offers the best combination of the pore volume retention and strength Example 5B
  • the primary purpose of using the lignin as a binder was to produce strong, attrition resistant, structures whilst using the minimum level of level of binder to reduce the loss in pore structure.
  • the lignin can however be used as microporous carbon precursor in its own right. The limitation is that it tends to partially melt and foam during carbonisation, see Figure 14.
  • this foaming characteristic can be completely eliminated through the addition of small amounts of the novolac resin, either as a cured resin powder or as the uncured novolac precursor, to give strong monolithic/extruded structures without the need for complex stabilisation by pre-oxidation.
  • Figure 13 shows the crush strength and weight loss for the carbonised TE7/20 resin - lignin composite monoliths through to the high lignin content formulations.
  • the weight loss is essentially independent of the lignin content confirming the similar process characteristics of the synthetic and natural phenolic resins.
  • the drop in strength at 80% lignin and higher is due to the foaming characteristic of the lignin during pyrolysis.
  • the structure of a monolith made from 100% lignin after pyrolysis is shown in Figure 14. It is clear that it is possible to make monoliths comprising almost entirely lignin as the precursor in the range 70-80% lignin.
  • Monolithic carbon structures have been produced using lignin as the second phase and milled natural precursors as the first phase.
  • Three materials have been evaluated as the first phase - rice husks, hemp shives and flax waste although the methods are equally applicable to other first phase materials.
  • the monoliths were carbonised in flowing carbon dioxide.
  • the furnace was ramped from ambient to 700°C at lC/minute and held for 10 minutes before cooling.
  • This can then be removed if required depending on the final applications. It can in principle be removed before or after activation by extraction with sodium hydroxide but if the monolith is to be activated it is preferably removed after activation as residual sodium catalyses the activation process and can cause problems. It can be removed by soaking the activated monolith in 1M NaOH solution for 5Hr at 80°C, rinsing with water and then repeating the extraction step.
  • the monolith is thoroughly washed to remove any residual sodium hydroxide or sodium silicate and then with 0.5M HC1 followed by further water washing. The monoliths were then thoroughly dried. After this process there was approx. 3% residual silica in the monoliths.
  • hemp shives may be processed as described above.
  • Bead materials were produced by the method described in WO 02/12380 where the resin components (novolac and HMTA), dissolved in ethylene glycol at ⁇ 100°C, are added to mineral oil at 150°C in the presence of a dispersant.
  • the mixture is mechanically stirred using a paddle stirrer and the size of the beads is primarily controlled by the stirrer rotation speed.
  • the temperature drops and the mixture is reheated to 150°C to complete the bead cure.
  • the beads are then filtered from the oil and thoroughly washed in hot water to remove the EG pore former. After drying the beads were carbonised in flowing carbon dioxide at 800°C.
  • the meso-macro pore structure of these carbons is controlled by the ratio of the total resin solids (novolac resin plus HMTA) to ethylene glycol.
  • the compositions are shown in the table below. As discussed above the mass of novolac and HMTA is kept constant and only the mass of ethylene glycol (EG) is varied. In the case of the novolac resin J1098F the composition varies between E3 and E6. The table also shows the nitrogen adsorption characteristics of these materials. It can be seen that the density of the J1098F based carbon decreases steadily as the EG content is increased reflecting the increased meso/macro pore volume. Across this range the BET area, which is predominantly present in the micropores remains essentially unchanged. At even higher EG levels (TE7 and TE9) but using a different feed resin (TPR210) the bulk density drops still further.
  • the pore structures of the J1098F derived carbons are shown in Figure 15 and show the steady increase in mean pore size and pore volume as the EG level is increased reaching a mean pore size of 800-900A.
  • the beads After filtration from the oil the beads are split into two fractions, the first of which is water washed 3 times with hot deionised water. The second fraction is vacuum dried at 160°C. After either washing or drying to remove the ethylene glycol pore former the porous resin is carbonised at 800°C in flowing carbon dioxide.
  • the actual TOSL4 formulation for the preparation was 80g novolac/20g OSL/20g HMTA/180g EG.
  • test data Whilst the majority of the test data is presented based on direct measurements of concentration vs time, the results have also been normalised by determining the challenge 0 removal and weight uptake on the carbon as a function of the number of passes through the monolith.
  • PCS and IS are both small molecules that can adsorb in the micropore structure of the carbons.
  • the rate of adsorption or removal is maximised for the smallest, 7mm, monoliths.
  • the kinetics of both the 18 and 28mm monoliths is significantly reduced. This difference in rate is also apparent for IL-6 ( Figure 24).
  • IL-6 Figure 24
  • the 25cm x ⁇ 30mm OD monoliths derived from 25 wt% lignin and 75 wt% TE7 resin prepared as in Examples 2 and 3 were mounted into the ends of large plastic syringes and sealed in place with shrink wrap tubing. This can be seen to the side of the pump system in Figure 20.
  • the monolith testing was carried out using both plasma and healthy donor whole bloods (400 ml from each donor) with sodium heparin anticoagulation purchased from Cambridge Bioscience Ltd (UK). These were then dosed with the challenge molecules.
  • the feed solution, blood or plasma, was continuously recycled from the reservoir through the column at 300ml/minute.
  • the monoliths were extruded using a 42mm die with a nominal 600cpi cell density as described in example 5A After drying the monolith was carbonised at 750C in flowing carbon dioxide and then activated at 850C in flowing carbon dioxide.
  • the donor blood was spiked with 5 mL of 33% ethanol per blood container (approximately 380 mL).
  • An erythrocyte suspension was used as donor blood, which was leucocyte-free.
  • the 'haemoperfusion' (HP) session was run for 60 minutes using the standard dialysis equipment at flow rate 140 mL/min (Fresenius). 22-24mm diameter carbon monoliths were used as described in (a). The results are shown in Table 7.
  • HP haemoperfusion
  • the biochemical parameters of blood remained unaffected by haemoperfusion over the carbon monolith.
  • SIRS systemic inflammatory response syndrome
  • SEB Staphylococcal enterotoxin B
  • the monolithic carbon is capable of removing the cytokine TNFa from both flowing blood (Figure 29) and flowing plasma (Figure 27) it is reasonable to assume that the SEB would also be removed using monoliths in place of beads in a haemoperfusion application.
  • ACLF Acute-on-Chronic Liver Failure
  • the beads were incubated with 5.4 ml of fresh human plasma spiked with 2 ⁇ /ml of phenol, 0.1 ⁇ /ml of tryptophan or cholic acid or 0.3 ⁇ /ml of bilirubin. 0.6ml samples were collected at 5,15, 30 and 60minutes and were analysed using standard test methods. Tests were carried out using 5 replicates.
  • the monoliths used in the tests were 7mm diameter, 95mm long, 25%weight lignin bound 600 cpi meso/macro porous monoliths as described in Example 5A.
  • the monoliths had a bimodal pore structure with lnm micropores and ⁇ 80nm macropores. This is identical to the A4 bead carbons used in (a).
  • Figure 33 shows that in agreement with the bead test data using spiked plasma, there is a steady reduction in the bilirubin content of the blood over the course of the 3 hour perfusion test. As bilirubin is the most difficult of the liver toxins to remove this clearly shows that the more easily adsorbed liver toxins should be easily removed from circulating blood using the macroporous monoliths.

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Abstract

Selon l'invention, une gamme de matériaux de carbone peut être produite au moyen de lignine en combinaison avec des résines phénoliques synthétiques ou se produisant naturellement dans des matériaux lignocellulosiques. La lignine, qui est sensiblement une résine phénolique se produisant naturellement, présente un rendement de carbone à la pyrolyse similaire à celui des résines synthétiques, ce qui aide au traitement. La lignine peut servir de phase de liant pour une résine synthétique ou des matériaux lignocellulosiques permettant la production de carbones monolithiques à partir d'une large gamme de précurseurs, de matériau structurel primaire dans lequel le traitement thermique est modifié par l'addition de petites quantités de matériaux de résine synthétique ou de structure modifiée dans la production de carbones mésoporeux/macroporeux sous forme de perle, de granulés ou sous forme monolithique. L'invention concerne un monolithe carbonisé comprenant des particules de carbone mésoporeuses et/ou macroporeuses dispersées dans une matrice de particules de carbone microporeuses, des vides entre les particules définissant de chemins de circulation de fluide dans et à travers la structure. Le monolithe peut prendre la forme d'un corps mis en forme dont les parois définissent une multiplicité de canaux de transport interne pour la circulation de fluide, les canaux de transport étant dirigés le long de la direction d'extrusion. Le monolithe peut être réalisé en carbonisant un corps phénolique mis en forme à base de précurseurs de résine phénolique. Selon un procédé de production de type corps de résine mis en forme pouvant être carbonisé, des particules solides d'une première résine phénolique qui est partiellement traitée thermiquement sont réalisées de sorte que les particules puissent être frittées mais ne fondent pas à la carbonisation. Les particules de la première résine phénoliques sont mélangées à des particules d'une deuxième résine phénolique dont le degré de traitement thermique est supérieur à celui de ladite première résine phénolique et dont la microstructure mésoporeux et/ou macroporeuse qui est préservée lors de la carbonisation. Le mélange résultant est formé en une pâte, par ex. en mélangeant les particules de résine avec de la méthylcellulose, du PEO et de l'eau, après quoi la pâte est extrudée pour former un produit mis en forme et en le stabilisant dans sa forme par frittage.
PCT/GB2016/052154 2015-07-16 2016-07-15 Corps nanoporeux mis en forme WO2017009662A1 (fr)

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CN107837793A (zh) * 2017-12-25 2018-03-27 郑州源冉生物技术有限公司 一种基于统糠的污水处理材料及其制备方法和应用
CN108503862A (zh) * 2018-03-05 2018-09-07 南京工业大学 一种超微木质素的制备方法
CN109650736A (zh) * 2018-04-19 2019-04-19 仲恺农业工程学院 一种超亲水增透涂层、制备方法和玻璃
WO2020101972A1 (fr) * 2018-11-12 2020-05-22 Dow Global Technologies Llc Support de catalyseur comprenant du carbone mésoporeux
CN115092927A (zh) * 2022-07-15 2022-09-23 安徽工程大学 碳纤维复材树脂基活性炭及其制备方法
SE2230267A1 (en) * 2022-08-17 2024-02-18 Stora Enso Oyj A method for producing a carbon material from lignin and a negative electrode comprising the carbon material

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CN106902858A (zh) * 2017-02-28 2017-06-30 济南大学 一种碳掺杂多孔石墨相氮化碳纳米分散体系的快速制备方法
CN107837793A (zh) * 2017-12-25 2018-03-27 郑州源冉生物技术有限公司 一种基于统糠的污水处理材料及其制备方法和应用
CN108503862A (zh) * 2018-03-05 2018-09-07 南京工业大学 一种超微木质素的制备方法
CN108503862B (zh) * 2018-03-05 2020-10-02 南京工业大学 一种超微木质素的制备方法
CN109650736A (zh) * 2018-04-19 2019-04-19 仲恺农业工程学院 一种超亲水增透涂层、制备方法和玻璃
WO2020101972A1 (fr) * 2018-11-12 2020-05-22 Dow Global Technologies Llc Support de catalyseur comprenant du carbone mésoporeux
CN115092927A (zh) * 2022-07-15 2022-09-23 安徽工程大学 碳纤维复材树脂基活性炭及其制备方法
CN115092927B (zh) * 2022-07-15 2023-06-20 安徽工程大学 碳纤维复材树脂基活性炭及其制备方法
SE2230267A1 (en) * 2022-08-17 2024-02-18 Stora Enso Oyj A method for producing a carbon material from lignin and a negative electrode comprising the carbon material
WO2024038399A1 (fr) * 2022-08-17 2024-02-22 Stora Enso Oyj Procédé de production d'un matériau carboné à partir de lignine
SE545992C2 (en) * 2022-08-17 2024-04-09 Stora Enso Oyj A method for producing a carbon material from lignin and a negative electrode comprising the carbon material

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